The Optical Anisotropies and the Mechanism of Vibronic Transitions in Spectra 4A2-2T2(2D) and 2E(2D) of Cs3CoBr5 and Cs3CoCl5 Studied by the Effect of Uniaxial Stress and the Zeeman Effect

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  • The Optical Anisotropies and the Mechanism of Vibronic Transitions in Spectra <SUP>4</SUP><I>A</I><SUB>2</SUB>→<SUP>2</SUP><I>T</I><SUB>2</SUB>(<SUP>2</SUP><I>D</I>) and <SUP>2</SUP><I>E</I>(<SUP>2</SUP><I>D</I>) of Cs<SUB>3</SUB>CoBr<SUB>5</SUB> and Cs<SUB>3</SUB>CoCl<SUB>5</SUB> studied by the Effect of Uniaxial Stress and the Zeeman Effect
  • Optical Anisotropies and the Mechanism

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The g⁄⁄-values of the excited Kramers doublets, spectral shifts by uniaxial stress and the optical anisotropies of all the absorption-lines in the spectra corresponding to the transition 4A2→2T2(2D) in Cs3CoBr5 and Cs3CoCl5 are investigated. The procedure of the assignment of the vibronic spectra is shown for the case that the electronic state is nearly degenerate and the vibronic interaction is weak enough to be treated by the perturbation method. The discrepancy in the assignment of vibronic lines in 4A2→2T2(2D) of Cs3CoBr5 between our result and Quested et al’s is shown to be due to the fact that the optical anisotropy and the MCD pattern do not reflect the symmetry of the electronic state but do that of the vibronic state. It is made clear from the optical anisotropy of vibronic lines that vibronic transitions in 4A2→2T2(2D) are allowed only by the aid of the even-parity vibronic interaction, while those in 4A2→2E(2D) are allowed not only by the even-parity vibronic interaction, but also by the odd-parity one.

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